Second Law of Thermodynamics Unwittingly Disproved by the Journal Nature

[Pentcho Valev]

"Here we find that Pt in a higher oxidation state (that is, PtO) demonstrates remarkable HOR suppression ability, while its hydrogen evolution capacity is still comparable to that of the benchmark of conventional metallic Pt cocatalyst through comprehensive experimental and theoretical analysis." Yu Hang Li et al. Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters https://www.nature.com/articles/ncomms3500

That is, the catalyst (PtO) accelerates the forward reaction, 2H+ -> H_2, but SUPPRESSES the reverse reaction, H_2 -> 2H+. Violation of the second law of thermodynamics par excellence. The picture in the paper is more than convincing:

http://images.nature.com/m685/nature-assets/ncomms/2013/130917/ncomms3500/images_hires/ncomms3500-f1.jpg

Pentcho Valev

[Pentcho Valev]

"In the presence of a catalyst, both the forward and reverse reaction rates will speed up EQUALLY... [...] If the addition of catalysts could possibly alter the equilibrium state of the reaction, this would violate the second rule of thermodynamics..." https://www.boundless.com/chemistry/textbooks/boundless-chemistry-textbook/chemical-equilibrium-14/factors-that-affect-chemical-equilibrium-106/the-effect-of-a-catalyst-447-3459/

Catalysts do not affect the forward and the reverse reaction rates EQUALLY - this is an absurd implication of the second law of thermodynamics. For instance, catalysts rhenium and tungsten affect the dissociation (H2 -> 2H) and the recombination (2H -> H2) reaction rates DIFFERENTLY:

"A small, closed, high temperature cavity contained two metal catalysts (rhenium and tungsten), which were known to dissociate molecular hydrogen (H2) to different degrees (Figure 1). (Rhenium dissociates hydrogen molecules into atoms better than tungsten does; conversely, tungsten recombines hydrogen atoms back into hydrogen molecules better than rhenium.) Because the dissociation reaction (H2 -> 2H) is endothermic (absorbs heat), and the recombination reaction (2H -> H2) is exothermic (liberates heat), when hydrogen was introduced into the cavity, the rhenium surfaces cooled (up to more than 125 K) relative to the tungsten (Figure 2). Because the hydrogen-metal reactions were ongoing in the sealed cavity, the rhenium stayed cooler than the tungsten indefinitely. This permanent temperature difference - this steady-state nonequilibrium - is expressly forbidden by the second law, not just because the system won't settle down to a single-temperature equilibrium, but because this steady-state temperature difference can, in principle, be used to drive a heat engine (or produce electricity) solely by converting heat back into work, which is a violation of one of the most fundamental statements of the second law (Kelvin-Planck formulation)." http://microver.se/sse-pdf/edgescience_24.pdf

Perpetual flow of the dimer A2 and the monomer A between two catalytic surfaces, S1 and S2 (time crystal par excellence):

http://upload.wikimedia.org/wikipedia/commons/c/ce/NatureSLTD-Fig1c.jpg

See the explanation here: https://en.wikipedia.org/wiki/Duncan%27s_Paradox

One of the absurd implications of the second law of thermodynamics is that, if a catalyst increases the rate constant of the forward reaction by a factor of, say, 745492, it obligatorily increases the rate constant of the reverse reaction by the same factor, 745492, despite the fact that the two reactions - forward and reverse - may be entirely different, e.g. the diffusion factor is crucial for one but not so important for the other. The absurd implication is usually referred to as "Catalysts do not shift chemical equilibrium":

"A catalyst reduces the time taken to reach equilibrium, but does not change the position of the equilibrium. This is because the catalyst increases the rates of the forward and reverse reactions BY THE SAME AMOUNT."
http://www.bbc.co.uk/bitesize/higher/chemistry/reactions/equilibrium/revision/2/

Scientists should have exposed the absurdity of this implication of the second law of thermodynamics long ago. How can the catalyst increase the rate constants of the forward and reverse reactions BY THE SAME AMOUNT if these two reactions are entirely different? Consider the dissociation-association reaction

A <-> B + C

which is in equilibrium. We add a catalyst, e.g. a macroscopic catalytic surface, and it starts splitting A - the rate constant of the forward (dissociation) reaction increases by a factor of 745492. If the second law of thermodynamics is obeyed, the catalyst must increase the rate constant of the reverse (association) reaction by exactly the same factor, 745492. But this is obviously absurd! The reverse reaction is entirely different from the forward one - B and C must first get together, via diffusion, and only then can the catalyst join them to form A. Catalysts don't accelerate diffusion! If, in the extreme case, the reverse reaction is diffusion-controlled, the catalyst cannot accelerate it at all - the rate constant already has a maximal and unsurpassable value.

The second law of thermodynamics is OBVIOUSLY false.

Pentcho Valev

[Pentcho Valev]

"Epicatalysis is a newly identified class of gas-surface heterogeneous catalysis in which specific gas-surface reactions shift gas phase species concentrations away from those normally associated with gas-phase equilibrium. As a result, epicatalytically created gas phase concentrations (in a sealed, isothermal cavity) can remain in a stationary nonequilibrium state. [...] A traditional catalyst adheres to three general principles, namely: 1) it speeds up a chemical reaction; 2) it participates in, but is not consumed by, the reaction; and 3) it does not change the chemical equilibrium of the reaction. Epicatalysts overcome the third principle when gas-surface interactions are appreciable and gas-phase collisions are rare. Under these conditions the gas particles that desorb from an epicatalytic surface can retain characteristics of the gas-surface interactions far away from the surface because gas phase collisions are too infrequent to establish normal gas phase equilibrium. Because gas-surface interactions dominate over gas-phase interactions in determining the gas-phase concentrations, the gas phase can be held, continuously, far away from normal gas phase equilibrium. Several well-studied examples of epicatalysis have been hiding in plain sight in scientific literature for nearly a century, including plasmas created by surface ionization, notably in the Q-machine; and hydrogen dissociation on high-temperature transition metals (e.g., W, Re, Mo, Re, Ir, and Ta). [...] Until recently, epicatalysis has been observed only at high temperatures (T > 1500 K) owing to the nature of their gas-surface reactions. (Covalent chemical bond energies and ionization energies for atoms are usually several electron volts.) However, as of 2015, epicatalysis has been observed at room temperature with molecules involving much weaker hydrogen-bonds (e.g., methanol, formic acid, water)." https://en.wikipedia.org/wiki/Epicatalysis

Unless the above is a series of blatant lies, the second law of thermodynamics has no place in science.

Pentcho Valev